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oai:docta.ucm.es:20.500.14352/1092142025-03-18T11:48:44Zcom_20.500.14352_14col_20.500.14352_15

00925njm 22002777a 4500 dc González Pinardo, Daniel author Bickelhaupt, F. Matthias author Fernández López, Israel author 2024 Quantum chemical calculations were carried out to quantitatively understand the origin of the Felkin–Anh(–Eisenstein) model, widely used to rationalize the π-facial stereoselectivity in the nucleophilic addition reaction to carbonyl groups directly attached to a stereogenic center. To this end, the possible approaches of cyanide to both (S)-2-phenylpropanal and (S)-3-phenylbutan-2-one have been explored in detail. With the help of the activation strain model of reactivity and the energy decomposition analysis method, it is found that the preference for the Felkin–Anh addition is mainly dictated by steric factors which manifest in a less destabilizing strain-energy rather than, as traditionally considered, in a lower Pauli repulsion. In addition, other factors such as the more favorable electrostatic interactions also contribute to the preferred approach of the nucleophile. Our work, therefore, provides a different, more complete rationalization, based on quantitative analyses, of the origin of this seminal and highly useful concept in organic chemistry. D. González-Pinardo, F. M. Bickelhaupt and I. Fernández, Origin of the Felkin–Anh(–Eisenstein) model: a quantitative rationalization of a seminal concept, Chem. Sci., 2024, 15, 12380–12387. 10.1039/d4sc03176h https://hdl.handle.net/20.500.14352/109214 https//doi.org/10.1039/d4sc03176h https://pubs.rsc.org/en/content/articlelanding/2024/sc/d4sc03176h Origin of the Felkin-Anh(-Eisenstein) Model: a Quantitative Rationalization of a Seminal Concept